Method of producing bodies of bituminous or tarry material



Patented Sept. 21, 4937 METHOD or rnonucma rumous on. 'rsnnx mas or m- ;rnamr.

Felix Jacohsolm, Berlin, Germany No Drawing. Application September 29, 1934, Serial No. 746,147. In Germany October- 30,

16 Claims.

The invention relates to a method of producing bodies of bitumen and tar, in particular for roads and underground construction. It is known to reduce the surface tension with respect to stone of tarand bitumen-bodies which are used in the construction ofroads and as insulating materials for waterproofing underground and foundation structures, by additions of various kinds, for example by distillation products from fossil prodv,ucts, which contain to a considerable extent bases with a strong nitrogen content. a

In the use of such nitrogen-containing substances, acti as covering media use is always made of be es of a different nature. As the result of systematic research it has been ascertained that not only the covering power but also the binding power of bituminous masses of every kind can be increased without the, addition of foreign substances. It is immaterial whether the tarand bitumen-mass is used in the form of an emulsionor diluted with solvents.

The increase in the coveringand bindingpower is. obtained by treating the materials to be improved in their technical properties at com- 5 paratively not too high temperatures with air or oxygen and at the same time adding a smallamount of'sulphuric acid of .2% to -3.0% by weight, which has a concentration of 66" Baum. With this treatment high molecular carboxylic The simultaneous reaction of sulphuric acid and air on petroleum asphalts. has already been proposed, but here considerably higher temperatures were used, to produce products of particularly high melting'point. Due to the greatly increased temperature complete decomposition took place of the added'sulphuric acid-used in larger quantities-and separation of the carboxyl group 5 from the carboxylic' acids and hydroxycarboxylic acids, hydroxycarboxylic acids and also sulphure I containing acids are preferably formed. In addl-- greater molecule than the substances which nor- In addition V acids occurred, whilein accordance with the in- I vention the additive compounds from constituents of the starting materials and of the 66 Baum sulphuric acid and the organic acids and oxy-acids formed for the most part remain and ensure that the road binding media produced coat the stone used in the road construction well and thereby firmly bind it, particularly in the' presence of the high molecular compounds formed by internal ring formation.

As another advantage it is to be considered that it is possible to employ an asphalt or tar product, .which at'flrst is in a freely flowing condition and then forms without hardening too quickly in the air, a very reliable, thin and uniform coating on the stone maerial, which coating is subjected to a gradual chemical change. The products may accordingly serve both.for the'surface treatment of the road as also--and this is technically particularly important-for coating road materials, such as brok emstones, chips, or the like, which ,are stored and 'laid on theroad at a suitable time. A further advantage of the process consists in this that with the use of a relatively very liquid bitumen oxidized by the blowing process one is independent of the weather. Even damp stone material is particularly satisfactorily coated, since then the formation of salts is somewhat accelerated, the oxidized masses producing an extraordinary and unforeseen penetrative effect. The effect caribe increased if mixtures of tars and asphalts are used, and it is immaterial what kinds of tars are used to provide the mixtures before or during the oxidation process. The method of producing is also applicable to shale and browncoal-tar. With coal tar it. is desirable. that it should be as free aspossible-from naphthalene, since this has often proved unsatisfactory on the road" and for foundation work. With material containing paraiiin, for example tars from brown coal, the oxidation should be carried out for a creased but generally even in this case 3% is sufllcient. I

In the further course of this work the quite surprising result has been found that a particularly advantageous effect is obtained if, inlieu of Quite extraordinary and unforeseen advantages.

have thereby been obtained; In theflrst place longer period and the acid addition somewhat in- .ptoduce increases in size of molecules and in viscosity, which can only be attained with the separate tars or petroleums after much longer distillation.

The residues of the simultaneous distillation especially possess a greater coveringand binding-action than apparently similar mixtures of residues obtained by separate distillations oi tars and petroleums. In particular it has been found that the mixed residues produced in accordance with the invention on treatment with air or oxygen and the simultaneous action of sulphuric'acid and other oxidizing and/or polymerizing substances produce much more quickly and at much lower temperature the desired end prod "ucts, the covering-' and binding-power of which is greater than with correspondingly treated mixtures of residues from separate distillations.

In all cases further improvements in the production and for different purposes may be obtained by a small addition of fatty oils, resin soaps, peroxides, or materials, which are used as drying agents in the paint industry and have an equivalent effect thereto.

All products produced in accordance with the described process can also be used either in the form of aqueous emulsions or diluted with solvents. j

In explanation of the operation of the processthe following examples will suflice:

Example 1 Kilograms Petroleum"asphalt i 700 Shale tar g 200 Coal tar-soft pitch 100 or only one of these substances are heated to 248 1". with stirring with dry steam. when the temperature is reached, the steam is gradually replaced by air. Steam is added only insuch quantity as is necessary to prevent excessive increase in temperature and minimize danger of fire. The issuing vapors are returned or condensed in suitable coolers and obtained as distillate. At about 266"'F. -2-10 kg. sulphuric acid having a concentration .of 66 Bau'me are added slowly. Part of the acid -e'scapes after reduction as sulphurous aid. when the product is broughtto the desired physical condition by oxidation and polymerization and internal ring formation, the air is shut oil and the substance itself, or in the form of an emulsion or diluted with solvents, used as roadconstruction or insulating-- and packing-material.

Example 2 g Kilograms Coal tar-soft pitch (prepared tar) 700 Petroleum asphalt; 200 Brown-coal-tar pitch are-mixed with 1-10 kg. linseed oil and 0.5 kg. manganese borate or 0.2 kg. cobalt oxide or litharge, the last mentioned addition being suitably ground previously with fatty oil. The mix- .ture is, as in the first example, heated o 5 1.

and blown with air under addition of about the same quantity of 66 Baum sulphuric acid and small quantities of persulphate, perborate, peracids, and the like, until a sumcient degree of oxidation and polymerization -is attained.

The duration of the blowing operation can obviously be varied within wide limits, according to the type of starting material and according to the desired consistency of the end product. As a guide it may be mentioned that in accordance with the invention there is obtainedafter a few hours, for example eight hours, and at temperatures slightly over 266 F. a material of consistency which can be obtained with the usual blowing methods onlyafter 24 hours and at much higher temperatures, without possessing the described valuable coveringand binding-properties. The times are only approximate and not given as limits.

Example 3 Example 4 With mixtures of brown coal tar and petroleum the appropriate starting material is obtained by removal of the solar oil or paraffin oil fraction.

In the further treatment of this residue the same advantages were obtained as regards time, temperature and properties as with Example 3.

I claim:

l. A process for obtaining a bituminous product comprising the steps of admixing an amount of .2% to 3.0% by weight of sulphuric acid to a tarry material, and blowing said mixture of a tarry material and sulphuric acid with a free oxygen containing gas at a temperature of about 266 F., said sulphuric acid having a strength sufflcient to form sulpho acids during the reaction.

. 2. A process for obtainingabituminousproduct comprising the steps of admixing an amount of 2%v to 3.0% by weight of sulphuric acid and oxidizing agents to a tarry material, and blowing the mass 'thus obtained with a free oxygen containing gas at a temperature of about 266. F., said sulphuric acid having a strength sumcient to form suipboacids during the reaction.

3. A process for obtaining an emulsifiable bituminous product comprising the steps of admixing an amount 01' .2% to 3.0% by weight of acid having a. strength suflicient to form sulpho acids during the reaction.

4. A process for obtaining a bituminous prodat a temperature of about 266 F., said sulphuric uct comprising the steps of admixing an amount of 2% to 3.0% by weight of sulphuric acid and e v a small amount of an oxidizing agent to a mixture of different bituminous materials, and blowing themass thusi'ormed with a free oxygen containing gas at a temperature of about 266 F.,

uct comprising the steps of admixing an amount of .2% to 3.0% by weight of sulphuric acid and gas at a temperature of about 266 F., said sulphuric acid having a strength suflicient to form sulpho acids during the reaction.

6. A process for obtaining a bituminous product comprising the steps of admixing an amount of .2% to 3.0% by weight of sulphuric acid and a; small amount of peracids to a mixture of different bituminous materials, and blowing the mass thus obtained with a free oxygen containing gas at a temperature of about 266 F., said sulphuric acid having a strength sufiicient to form sulpho acids during the reaction. I

7. A process for obtaining a bituminous product comprising the steps of admixing an amount of .2% to 3.0% by weight of sulphuric acid and a small amount of a salt of a peracid to a mixture of different bituminous materials, and blowing 8. A process for obtaining a bituminous product comprising the steps of admixing an amount of .2% to 3.0% by weight of sulphuric acid and a small amount of a drying agent to a mixture of different bituminous materials, and blowing the mass thus obtained with a i'reeoxygen containing gas at a temperature of about 266 F.,

said sulphuric acid having a strength suflicient thus formed with a free oxygencontaining gas at a temperature of about 266 F., said sulphuric acid having a strength suillcient to form sulpho acids during the reaction.

1 0. A process for obtaining abituminous product comprising the steps of admixing an amount of .2% to 3.0% by weight of sulphuric acid to a mixture of difierent tars and petroleum, and blowing the mass thus obtained with a free oxygen containing gas at a temperature of about 266 F.,

. sulphur content.

said sulphuric acid having a strength suillcient to form sulpho acids during the reaction.

11. A process for obtaining a bituminous product comprising the steps of simultaneously distilling a mixture of difl'erent tars, admixing an amount of .2% to 3.0% by'weight of sulphuric acid to the residues obtained by said distillation, and blowing said mixture of said residues and sulphuric acid with a free oxygen containing gas at a temperature of about 266 F., said sulphuric acid having a strength sumcient to form sulpho acids during the reaction.

12. A process for obtaining a bituminousproduct comprising the steps of simultaneously distilling a mixture of at least one tar and petroleum, admixing an amount of .2% to 3.0% by weight of sulphuric acid to the residues obtained by said distillation, and blowing said mixture of said residues and sulphuric acid with a free oxygen containing gas at a temperature of about 266 F., said sulphuric acid having a strength suilicie'nt to form sulpho acids during the reaction. r

13. A process according to claim 12 in which said petroleum is a petroleum having a high 14. A bituminous product obtained by blowing with a free oxygen containing gas at a temperature.o f about 266 F. a. mixture containing a bituminous material and an amount of .2% to 3.0% by weight of sulphuric acid having a strength suflicient to form sulpho acids during the reaction.

15. An emulsiflable bituminous product ob-v tained by blowing with a free oxygen containing gas at a temperature of about 266 F. a mixture containing a mixture of different bituminous materials and an amount of .2% to 3.0% by weight of sulphuric acid having a strength sufllclent to form sulpho acids during the reaction.

' 16. A bituminous product obtained by blowing with a free oxygen containing gas at a tempera- 

